JPH10186699A - Light receiving member for electrophotography - Google Patents

Abstract

[PROBLEMS] Light having excellent electric potential characteristics and image characteristics by reducing optical memory when using an LED as a light source for exposure, reducing temperature physical properties of sensitivity, and improving sensitivity linearity. A receiving member is provided. SOLUTION: A conductive support and a photoconductive layer made of a non-single-crystal material containing a hydrogen atom and / or a halogen atom based on a silicon atom and exhibiting photoconductivity are provided on a surface of the conductive support. In the light receiving layer having at least the light receiving member and the light receiving member having at least the light receiving layer, the photoconductive layer has a hydrogen atom and / or halogen atom content (Ch) of 10 atom% or more and 20 atom% or more.
Atomic% or less, optical band gap (Eg) is 1.65
It has a first layer region and a second layer region having different characteristic energies (Eu) obtained from the exponential function tail of the light absorption spectrum from eV to 1.75 eV, and the characteristic energy of the first layer region ( Eu) is 60 meV or more and 70 meV or less, and the characteristic energy (Eu) of the second layer region is 50 meV.
It is configured so that it is not less than V and not more than 60 meV.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to light (here, light in a broad sense, meaning ultraviolet light, visible light, infrared light, X-rays, .gamma.-rays, etc.). The present invention relates to a light receiving member for photography.

[0002]

2. Description of the Related Art In the field of image formation, photoconductive materials for forming a light receiving layer in a light receiving member for electrophotography include:
High sensitivity, SN ratio [photocurrent (Ip) / dark current (Id)]
Characteristics, such as high absorption, having an absorption spectrum suitable for the spectral characteristics of the electromagnetic wave to be irradiated, fast light response, having a desired dark resistance value, and being harmless to the human body during use. Is done. In particular, in the case of an electrophotographic light-receiving member incorporated in an electrophotographic apparatus used in an office as an office machine, the above-described non-polluting property at the time of use is important.

[0003] Hydrogenated amorphous silicon (hereinafter referred to as "a-Si:
H "). For example, Japanese Patent Publication No. 60-350
No. 59 describes an application as a light receiving member for electrophotography.

As a method of forming such a light receiving member for electrophotography, a conductive support is heated to 50 ° C. to 350 ° C., and a vacuum deposition method, a sputtering method, an ion plating method, a heat A method of forming a photoconductive layer made of a-Si by a film forming method such as a CVD method, a photo CVD method, and a plasma CVD method is generally used. Above all, plasma CV
Method D, that is, a method in which a raw material gas is decomposed by high-frequency or microwave glow discharge to form an amorphous silicon (a-Si) deposited film on a support has been put to practical use as a suitable method.

Japanese Patent Application Laid-Open No. 56-83746 discloses an electrophotographic light receiving member comprising a conductive support and an a-Si (a-Si: X) photoconductive layer containing a halogen atom as a constituent element. Has been proposed. In this publication, a-Si contains from 1 to 40 at% of halogen atoms, whereby heat resistance is high and good electrical and optical characteristics can be obtained as a photoconductive layer of a light receiving member for electrophotography. I can do it.

Japanese Patent Application Laid-Open No. S57-115556 discloses that a photoconductive member having a photoconductive layer composed of an a-Si deposited film has electrical and electrical properties such as dark resistance, photosensitivity and photoresponsiveness.
In order to improve the use environment characteristics such as optical and photoconductive properties and moisture resistance, as well as the stability over time, silicon atoms and carbon atoms are formed on a photoconductive layer composed of an amorphous material containing silicon atoms as a base material. A technique for providing a surface barrier layer made of a non-photoconductive amorphous material containing is described. Further, Japanese Patent Application Laid-Open No. 62-168161 discloses that a silicon atom and a carbon atom
A technique using an amorphous material containing ７０70 atomic% of hydrogen atoms as a constituent element is described.

Further, Japanese Patent Application Laid-Open No. 62-83470 discloses a photoconductive layer of an electrophotographic photoreceptor in which the characteristic energy of the exponential function of the light absorption spectrum is set to 0.09 eV or less so that the afterimage phenomenon is prevented. Techniques for obtaining quality images are described.

Japanese Patent Application Laid-Open No. 58-21257 discloses that the bandgap in the photoconductive layer is changed by changing the temperature of the support during the formation of the photoconductive layer, and the photoconductive layer has a high resistance and high photosensitivity. A technique for obtaining a photosensitive member having a wide area is described. Japanese Patent Application Laid-Open No. 58-67022 discloses a technique of stacking layers having different mixing ratios of SiH ₄ gas and H ₂ gas to obtain a photosensitive material having high charging ability and high sensitivity. A technique for obtaining a body is described,
JP-A-43379 and JP-A-61-201481 describe a technique for obtaining a photosensitive member having high dark resistance and high sensitivity by laminating a-Si: H having different hydrogen contents.

On the other hand, Japanese Patent Application Laid-Open No. 60-95551 discloses that in order to improve the image quality of an amorphous silicon photoreceptor, the temperature near the surface of the photoreceptor is maintained at 30 to 40.degree. By performing such an image forming process, there is described a technique for preventing a reduction in surface resistance due to the adsorption of moisture on the surface of a photoreceptor and an image deletion caused thereby.

[0010] These techniques have improved the electrical, optical, photoconductive and operating environment characteristics of the electrophotographic light-receiving member, and accordingly the image quality.

[0011]

However, a conventional electrophotographic light-receiving member having a photoconductive layer made of an a-Si-based material has a low electrical resistance such as dark resistance, photosensitivity and photoresponsiveness. In terms of optical, photoconductive, and use environment characteristics, and further, stability with time and durability, each of the characteristics has been sufficiently improved, but the overall characteristics are to be improved. In fact, there is room for further improvement.

In particular, high image quality, high speed, and high durability of an electrophotographic apparatus are rapidly progressing. In a light receiving member for electrophotography, the electric property and the photoconductive property are further improved, and the chargeability, There is a need to significantly increase performance in all environments while maintaining sensitivity.

As a result of the improvement of the optical exposure device, the developing device, the transfer device and the like in the electrophotographic apparatus in order to improve the image characteristics of the electrophotographic apparatus, the image receiving properties of the electrophotographic photoreceptor member have been improved. Has been required to be improved.

Under such circumstances, the above-mentioned prior art has made it possible to improve the above-mentioned problems to some extent. However, in order to further expand the application range of the electrophotographic photoreceptor, charging performance and image quality have to be improved. There have been cases where the improvement of the quality has not been sufficient. In particular, as an issue for further improving the image quality of the amorphous silicon light receiving member,
It has become even more demanded to reduce variations in electrophotographic characteristics due to changes in ambient temperature and optical memories such as blank memories and ghosts.

For example, conventionally, as described in JP-A-60-95551, a drum heater is installed in a copying machine to reduce the surface temperature of the photosensitive member to 40 to prevent image deletion on the photosensitive member. ℃ was maintained. Even during the night when the copying machine is not used, the drum heater is energized to prevent the ozone product generated by the corona discharge of the charger from adsorbing on the surface of the photoconductor at night, thereby preventing the image flow caused by the ozone product. However, now, resource saving,
In order to save power, the power supply to the copier at night has been reduced as much as possible. When copying is performed in such a state, there has been a problem that the temperature around the photosensitive member in the copying machine gradually increases, and the image density changes accordingly.

Further, when the same original is continuously and repeatedly copied, an afterimage of image exposure in the previous copying process causes a so-called ghost to occur on an image at the next copying, and a paper interval during continuous copying to save toner. However, there has been a problem in that the quality of the image is further improved by more strictly preventing a blank memory or the like in which a density difference occurs on a copied image due to the influence of a so-called blank exposure, which is applied to a photosensitive member.

In addition, the electrophotographic apparatus has been required to be digitized in order to fulfill the role of a facsimile or a printer as well as a conventional copying machine. The mainstream of semiconductor lasers and LEDs (light emitting diodes) mainly used as light sources for exposure for this purpose are those having a relatively long wavelength from near infrared to red visible light in terms of emission intensity and price. For this reason, it has been demanded to improve the characteristic problem which has not been seen in the analog machine using the conventional halogen light as the light source for exposure.

A characteristic feature of the use of an LED having a distribution of emission wavelengths as compared with a semiconductor laser is that the relationship between the exposure amount (E) and the photoconductor surface potential (V), that is, the so-called EV curve depends on the temperature. Attention has been paid to the shift (temperature characteristics of sensitivity) and the poor linearity of the EV curve (linearity of sensitivity).

That is, in a digital device using an LED as a light source for exposure, the sensitivity changes depending on the ambient temperature and the image density changes due to an increase in sensitivity temperature characteristics and a decrease in sensitivity linearity. Issues have arisen.

Therefore, when designing a light-receiving member for electrophotography, from the comprehensive viewpoint such as the layer structure of the light-receiving member for electrophotography and the chemical composition of each layer so as to solve the above-mentioned problems. Along with further improvement, it is necessary to further improve the characteristics of the a-Si material itself.

An object of the present invention is to solve the above-described various problems in the electrophotographic light-receiving member having the light-receiving layer made of a-Si.

That is, the main object of the present invention is to improve the temperature characteristics of sensitivity and the linearity of sensitivity to dramatically reduce the amount of optical memory and improve the image quality even when an LED is used as a light source for image exposure. An object of the present invention is to provide an electrophotographic light receiving member having a light receiving layer formed of a non-single-crystal material having silicon atoms as a base.

The electrical, optical, and photoconductive properties are substantially always stable without depending on the use environment, are excellent in light fatigue resistance, and do not cause deterioration and development when repeatedly used. To provide an electrophotographic light-receiving member having a light-receiving layer composed of a non-single-crystal material based on silicon atoms, which has excellent moisture resistance, hardly any residual potential is observed, and has good image quality. is there.

[0024]

Means for Solving the Problems To solve the above-mentioned problems, the present inventors focused on the behavior of carriers in the photoconductive layer, and studied the distribution of localized state density in the band gap of a-Si and the temperature characteristics. As a result of intensive studies on the relationship with the optical memory and the optical memory, the above object can be achieved by controlling the hydrogen content, the optical band gap and the distribution of the localized state density in the band gap in the thickness direction of the photoconductive layer. I got the knowledge. That is, in an electrophotographic light-receiving member having a photoconductive layer composed of a non-single-crystal material containing a silicon atom as a base and a hydrogen atom and / or a halogen atom, it is designed to specify the layer structure. It has been found that the light receiving member for electrophotography prepared as described above has not only excellent properties in practice but also excellent properties as a light receiving member for electrophotography.

In particular, sensitivity is controlled by controlling the hydrogen content, the optical band gap, and the distribution of localized state densities in the band gap at the light incident portion related to photoelectric conversion when an LED is used as a light source for image exposure. It was found that the temperature characteristics and the linearity of sensitivity could be improved.

Furthermore, the uniformity of image density (so-called roughness) can be improved by controlling the hydrogen content in the interface region with the blocking layer, the optical band gap, and the distribution of the local density of states in the band gap. While you can
It has been found that the adhesion to the blocking layer can be improved.

Accordingly, the present invention provides an invention having the following features.

That is, a first embodiment of the light receiving member for electrophotography according to the present invention is a conductive support, and a hydrogen atom and / or a halogen atom provided on the conductive support and containing a silicon atom. And a photoconductive layer made of a non-single-crystal material having, as a base, a photoconductive layer for electrophotography, wherein the photoconductive layer has a content of hydrogen atoms and / or halogen atoms (Ch) and an optical band gap (Ch). Eg) is 1
0 atomic% or more and 20 atomic% or less, 1.65 eV or more and 1.7
5eV or less, a function represented by the formula (I) Inα = (1 / Eu) · hν + α ₁ (I) where photon energy (hν) is an independent variable and absorption coefficient (α) of a light absorption spectrum is a dependent variable. It has a first layer region and a second layer region having different characteristic energies (Eu) obtained from the linear relationship portion (exponential function tail), and Eu of the first layer region is 60
not less than meV and not more than 70 meV, and E of the second layer region
The light receiving member for electrophotography, wherein u is not less than 50 meV and not more than 60 meV. Note that Eu in the first layer region is set to be larger than Eu in the second layer region.

According to a second aspect of the present invention, the photoconductive layer comprises:
The first layer region and the second layer region are arranged in this order from the conductive support side, and the film thickness of the second layer region is 50% to 95% of the incident light. Is a light-receiving member for electrophotography that has a thickness that absorbs light.

[0030] In a third aspect of the present invention, the photoconductive layer comprises:
From the conductive support side, the second layer region having a layer thickness of 0.1 to 5 μm, the first layer region, and the layer thickness were set to absorb 50% to 95% of incident light. An electrophotographic light-receiving member having a configuration in which the second layer regions are arranged in this order.

A fourth aspect of the present invention is a light-receiving member for electrophotography, wherein the photoconductive layer contains at least one element belonging to Group IIIb or Group Vb of the periodic table.

A fifth aspect of the present invention is a light-receiving member for electrophotography, wherein the photoconductive layer contains at least one of carbon, oxygen and nitrogen.

According to a sixth aspect of the present invention, the photoconductive layer is made of a silicon-based non-single-crystal material containing a hydrogen atom and / or a halogen atom and containing at least one of carbon, oxygen and nitrogen. It is an electrophotographic light-receiving member provided with a surface layer.

According to a seventh aspect of the present invention, the photoconductive layer comprises:
On a charge injection blocking layer made of a non-single-crystal material containing a silicon atom as a base and containing at least one of carbon, oxygen and nitrogen, and at least one element selected from Group IIIb or Group Vb of the Periodic Table. An electron, wherein a surface layer made of a silicon-based non-single-crystal material containing a hydrogen atom and / or a halogen atom and containing at least one of carbon, oxygen and nitrogen is provided on the photoconductive layer. It is a light receiving member for photography.

According to an eighth aspect of the present invention, in the sixth or seventh aspect, the thickness of the surface layer is 0.01 to 3 μm.
m is a light receiving member for electrophotography.

A ninth aspect of the present invention is the electrophotographic light-receiving member according to the seventh aspect, wherein the charge injection blocking layer has a thickness of 0.1 to 5 μm.

A tenth aspect of the present invention is a light-receiving member for electrophotography, wherein the photoconductive layer has a thickness of 20 to 50 μm.

The term "exponential function tail" used in the present invention refers to an absorption spectrum obtained by subtracting the tail from the absorption of the light absorption spectrum to the lower energy side. ) "Means the slope of the exponential function tail.

This will be described in detail with reference to FIG.

FIG. 1 is an example of a sub-gap light absorption spectrum of a-Si in which the horizontal axis represents the photon energy hν and the vertical axis represents the absorption coefficient α on the logarithmic axis. This spectrum is roughly divided into two parts. That is, a portion B in which the absorption coefficient α changes exponentially, that is, linearly with the photon energy hν, that is, a so-called exponential function tail or Urb.
The ach tail and the portion A where α has a more gradual dependence on hν.

The B region corresponds to light absorption due to an optical transition from the tail level on the valence band side to the conduction band in a-Si.
The exponential dependence of the absorption coefficient α of the region on hν is expressed by the following equation.

[0042] _{α = α 0 exp (hν /} Eu) and taking the logarithm of the both sides lnα = (l / Eu) · hν + α 1 However, α ₁ = lnα _0, and the inverse of the characteristic energy Eu (1 / Eu) is , B portion. E
Since u corresponds to the characteristic energy of the exponential energy distribution of the tail level on the valence band side, a small Eu means that the tail level on the valence band side is small.

The temperature characteristics of sensitivity and the linearity of sensitivity used in the present invention will be described with reference to FIG.

FIG. 2 shows that, at room temperature (drum heater OFF) and at about 45 ° C. (drum heater ON), the photosensitive member is charged so as to have a surface potential of 400 V as a dark potential. L of 680mm
This is an example of a change in surface potential (bright potential) when ED irradiation is performed and the amount of exposure is changed, so-called EV characteristics (curve).

The temperature characteristic of the sensitivity is such that when the difference between the dark potential and the bright potential becomes 200 V (Δ200: 200 V position on the vertical axis obtained by subtracting 200 V from 400 V), the room temperature of the exposure amount (half reduction exposure amount) And the value at about 45 ° C.

The linearity of sensitivity is obtained when the difference between the dark potential and the bright potential is 350 V (Δ350: 400 V to 350 V).
V350 is extrapolated by a straight line connecting the exposure amount (actually measured value) of the vertical axis obtained by subtracting V and the point without exposure (dark state) and the point irradiated with the half-exposure amount. Is defined as the difference from the exposure amount (measured value). In any case, it means that the smaller the value is, the better the characteristics of the photoreceptor are.

The present inventors have proposed an optical band gap (hereinafter abbreviated as “Eg”) and a constant photocurrent method (Co
nstant Photocurrent Metho
d: abbreviated as CPM) to investigate the correlation between the characteristic energy (Eu) of the exponential function tail (Erbuck tail) obtained from the sub-bandgap light absorption spectrum and the photoreceptor characteristics over various conditions. As a result, E
The inventors have found that there is a close relationship between g, Eu and the charging ability, temperature characteristics and optical memory of the a-Si photosensitive member, and have completed the present invention.

Further, as a result of a detailed study of the characteristics of the semiconductor photosensitive member and Eg, Eu at the light incident portion when an LED is used as the image exposure light source, the temperature characteristics of Eg, Eu, the sensitivity, and the linearity of the sensitivity were found. And found that they had a close relationship,
The inventors have found that by controlling Eu within a specific range, the photosensitive member characteristics suitable for light having a relatively long wavelength are exhibited, and the present invention has been completed.

That is, a layer region where the optical band gap is relatively small and the capture ratio of carriers to localized levels is reduced is disposed in the interface region between the photoconductive layer and the surface layer to form a photoelectric conversion portion. Thus, the present inventor has found that the temperature characteristics can be reduced while the charging performance is improved, the optical memory can be substantially eliminated, and the temperature characteristics of sensitivity and the linearity of sensitivity can be significantly improved. These experiments revealed this.

Further, by arranging a layer region having a low hydrogen content and a small trapping ratio of carriers to localized levels in the interface region with the blocking layer, the optical memory can be reduced and the image density can be reduced. It has also been found that the uniformity (so-called roughness) can be improved, and that the improvement in adhesion can sufficiently cope with an increase in stress accompanying lamination on a small-diameter support.

This will be described in more detail. In general, the band gap of a-Si: H is Si-Si: H.
The tail (tail) level based on the structural disorder of the bond and S
There is a deep level due to a structural defect such as a dangling bond of i. It is known that these levels function as trapping and recombination centers for electrons and holes, and cause deterioration of device characteristics.

As a method of measuring the state of the localized level in such a band gap, generally, a deep level spectroscopy, an isothermal capacity transient spectroscopy, a photothermal deflection spectroscopy, a photoacoustic spectroscopy, a constant photocurrent method, etc. Is used. Among them, the aforementioned CPM is
This is useful as a method for easily measuring a subgap light absorption spectrum based on a localized level of a-Si: H.

The optical memory is generated when optical carriers generated by blank exposure or image exposure are trapped at localized levels in the band gap, and the carriers remain in the photoconductive layer. That is, of the photocarriers generated in a certain copying process, the carriers remaining in the photoconductive layer are swept out by the electric field due to the surface charge at the next charging or thereafter, and the potential of the light-irradiated portion is changed to the other. Lower than the area, resulting in shading on the image. Therefore, in order to prevent the occurrence of the optical memory, it is necessary to improve the traveling properties of the optical carrier so that the optical carrier travels in one copying process without remaining in the photoconductive layer as much as possible.

Further, the temperature characteristic of the sensitivity is caused by a large difference between the traveling properties of the electrons and the holes in the photoconductive layer, and also because the traveling properties vary depending on the temperature. In the light incident portion, carriers (electron-hole pairs) are generated. In the case of positive charging, electrons travel to the surface layer side and holes travel to the support side. In the LED, however, the wavelength and the absorption coefficient of a-Si are compared. Due to the relationship, light penetrates deeply and the region where carriers are generated becomes thick. If holes and electrons are mixed at the light incident portion, the ratio of recombination before reaching the support or the surface increases. Since the recombination ratio changes due to thermal excitation from the capture center, the exposure dose, that is, the number of photogenerated carriers and the number of carriers that cancel the surface potential, change with temperature, and as a result, the sensitivity changes with temperature. Becomes Therefore, the rate of recombination at the light incident portion is reduced, that is, the deep level serving as a capture center is reduced, and the light absorption rate is increased so that the mixed region of holes and electrons is reduced as much as possible.
In addition, the traveling performance of the carrier must be improved.

Further, the linearity of the sensitivity is such that the number of photo-generated carriers relatively deep from the surface increases as the exposure amount of the LED increases, and the carriers (positively charged) required to cancel the surface charge are increased. In some cases, this occurs because the traveling distance of electrons increases. Therefore, it is necessary to improve the light absorptance of the light incident part and to improve and balance the electron traveling property and the hole traveling property of the light incident part.

Therefore, by providing a layer region in which Eu is controlled (reduced) while decreasing Ch and narrowing Eg as a light incident portion, the rate at which thermally excited carriers and photocarriers are captured in localized levels can be reduced. Since the size can be reduced, the traveling property of the carrier is improved. By reducing Eg, the absorption of long-wavelength light is increased and the light incident portion can be thinned, so that the mixed region of holes and electrons can be reduced. Further, the support-side photoconductive layer can be designed as a layer in which the main carrier is holes and the traveling property is improved.

That is, in the present invention, the first layer region is a main photoconductive layer, and the second layer region is provided on the surface side, and the region that substantially absorbs light is the second layer region. Accordingly, the effect that the temperature characteristics of sensitivity and the linearity of sensitivity are greatly improved particularly when an LED is used as a light source for image exposure is recognized. Further, by providing a second layer region in which Eu is controlled (reduced) while reducing Ch and narrowing Eg, the blocking layer side is further provided as necessary, so that the ratio of photocarriers trapped in the localized level can be improved. Can be greatly reduced, the traveling property of the carrier is dramatically improved, and the unevenness (graininess) of the minute image density is reduced, and the adhesion to the support or the blocking layer is improved. This also facilitates application to a small-diameter support. That is, by providing the second layer region also on the support side, a more remarkable effect can be recognized in terms of the prevention of roughening and the improvement in adhesion.

That is, according to the present invention, all of the above-mentioned problems in the prior art can be achieved by the above-described structure, by reducing optical memory, reducing sensitivity temperature characteristics, improving sensitivity linearity, improving image density unevenness and improving adhesion. Can be solved, and a light-receiving member exhibiting extremely excellent electrical, optical, and photoconductive properties, image quality, durability, and use environment can be obtained.

The wavelength characteristic of the LED as an exposure light source applied to the light receiving member of the present invention has a center wavelength preferably in the range of 600 to 750 nm, more preferably in the range of 680 to 700 nm. Things can be mentioned.

[0060]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The electrophotographic light-receiving member of the present invention will be described below in detail with reference to the drawings.

FIG. 3 is a schematic structural view for explaining the layer constitution of the electrophotographic light-receiving member of the present invention.

The light receiving member 3 for electrophotography shown in FIG.
In No. 00, a light receiving layer 302 is provided on a conductive support 301 for a light receiving member for electrophotography. The light receiving layer 302 is made of amorphous silicon (a) containing hydrogen atoms (H) and / or halogen atoms (X).
—Si: H, X) and a photoconductive layer 3 having photoconductive properties
The photoconductive layer 303 includes a first layer region 311 and a second layer region 312 in this order from the support 301 side.

The electrophotographic light receiving member 3 shown in FIG.
In No. 00, a light receiving layer 302 is provided on a conductive support 301 for a light receiving member for electrophotography. The light receiving layer 302 is composed of a photoconductive layer 303 made of a-Si: H, X and having photoconductivity.
Reference numeral 3 denotes a second layer region 312 and a first layer region 312 in order from the support 301 side.
Layer region 311 and a second layer region 312.

The light receiving member 3 for electrophotography shown in FIG.
In No. 00, a light receiving layer 302 is provided on a conductive support 301 for a light receiving member for electrophotography. The light receiving layer 302 is composed of a photoconductive layer 303 made of a-Si: H, X and having photoconductivity, and an amorphous silicon-based surface layer 304. The photoconductive layer 303 is composed of a first layer region 311 and a second layer region 312 in order from the support 301 side. Also, the support 3
01 second layer region 312, first layer region 31
First and second layer regions 312 can be used.

The light receiving member 3 for electrophotography shown in FIG.
In No. 00, a light receiving layer 302 is provided on a conductive support 301 for a light receiving member for electrophotography. The light receiving layer 302 includes an amorphous silicon-based charge injection blocking layer 305 and an a-Si:
It is composed of a photoconductive layer 303 made of H and X and having photoconductivity, and an amorphous silicon-based surface layer 304. The photoconductive layer 303 is composed of a first layer region 311 and a second layer region 312 in order from the charge injection blocking layer 305 side. In addition, a second layer region 312, a first layer region 311, and a second layer region 312 can be formed in this order from the charge injection blocking layer 305 side. <Support> The conductive support used in the present invention may be any as long as it has the conductivity required for an electrophotographic photosensitive member on the surface on which the light receiving layer is provided, and is made of a conductive material itself. A substrate or a substrate provided with conductivity on a predetermined surface of an electrically insulating substrate can be used. As the conductive material, Al, Cr, Mo, Au, In, Nb,
Examples include metals such as Te, V, Ti, Pt, Pd, and Fe, and alloys thereof, such as stainless steel. Also,
Examples of the electrically insulating substrate include polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polystyrene, synthetic resin films or sheets such as polyamide, glass, and ceramics. A support obtained by conducting a conductive treatment on at least the surface of the electrically insulating substrate on which the light receiving layer is to be formed can be used.

The shape of the support 301 used in the present invention may be a cylindrical or endless belt having a smooth surface or an uneven surface, and the thickness thereof may be such that the light receiving member 300 can be formed as desired. When the flexibility of the light receiving member 300 is required, the thickness can be made as thin as possible within a range where the function as the support 301 can be sufficiently exhibited. However, the support 30
1 is usually 10 μm or more in terms of production, handling, mechanical strength and the like. <Photoconductive layer> In the present invention, in order to effectively achieve the object, a photoconductive layer 302 is formed on a support 301.
The photoconductive layer 303 which constitutes a part of is formed by a vacuum deposition film forming method, in which numerical conditions of film forming parameters are appropriately set so as to obtain desired characteristics. Specifically, for example, a glow discharge method (low-frequency CVD method, high-frequency CV
AC discharge CVD method such as D method or microwave CVD method,
Or a direct current discharge CVD method), a sputtering method, a vacuum deposition method, an ion plating method, a photo CVD method, and a heat C method.
It can be formed by various thin film deposition methods such as a VD method. These thin film deposition methods are appropriately selected and adopted depending on factors such as manufacturing conditions, the degree of load under capital investment, the manufacturing scale, and the characteristics desired for the light-receiving member to be produced. The glow discharge method, particularly the high-frequency glow discharge method using a power frequency in the RF band, is suitable because the conditions for manufacturing the light receiving member are relatively easy to control.

In order to form the photoconductive layer 303 by the glow discharge method, a source gas for supplying Si that can supply silicon atoms (Si) and a source gas for supplying H that can supply hydrogen atoms (H) are basically used. Is introduced in a desired gas state into a reaction vessel in which the inside can be reduced in pressure, and a glow discharge is generated in the reaction vessel. A-Si: on a predetermined support 301 previously installed at a predetermined position.
What is necessary is just to form the layer which consists of H and X.

In the present invention, it is necessary for the photoconductive layer 303 to contain hydrogen atoms and / or halogen atoms, which traps dangling bonds of silicon atoms and improves the quality of the layer. This is because it is indispensable to improve photoconductivity and charge retention characteristics. Therefore, the total content of hydrogen atoms and halogen atoms (when hydrogen atoms or halogen atoms are contained alone, the respective contents) (Ch) is desirably 10 atomic% or more and 20 atomic% or less. .

The substances that can be used as the Si supply gas used in the present invention include SiH ₄ , Si ₂ H ₆ , Si ₃ H
_8. Silicon hydrides (silanes) in a gas state such as Si ₄ H ₁₀ or capable of being gasified are effectively used, and furthermore, such as ease of handling at the time of forming a layer, high Si supply efficiency, etc. In this respect, SiH ₄ and Si ₂ H ₆ are preferred.

Then, hydrogen atoms are structurally introduced into the photoconductive layer 303 to be formed, and the control of the introduction ratio of hydrogen atoms is further facilitated to obtain film characteristics which achieve the object of the present invention. Therefore, it is necessary to form a layer by mixing a desired amount of H ₂ and / or He or a silicon compound gas containing a hydrogen atom with these gases. Further, each gas is not limited to a single species, and a plurality of species may be mixed at a predetermined mixture ratio.

The source gas for supplying a halogen atom used in the present invention may be, for example, a gas or a gas such as a halogen gas, a halide, an interhalogen compound containing a halogen, or a silane derivative substituted with a halogen. The obtained halogen compounds are preferred. Further, a gaseous or gasifiable silicon hydride compound containing a halogen atom, which contains a silicon atom and a halogen atom as constituent elements, can also be mentioned as an effective compound. Specific examples of the halogen compound that can be suitably used in the present invention include fluorine gas (F ₂ ), BrF,
Examples thereof include interhalogen compounds such as ClF, ClF ₃ , BrF ₃ , BrF ₅ , IF ₃ , and IF ₇ . Specific examples of the silicon compound containing a halogen atom, ie, a silane derivative substituted with a halogen atom, include, for example, SiF
₄ , silicon fluorides such as Si ₂ F ₆ are preferred.

In order to control the amount of hydrogen atoms and / or halogen atoms contained in the photoconductive layer 303, for example, the temperature of the support 301, a raw material used for containing hydrogen atoms and / or halogen atoms, etc. What is necessary is just to control the amount of the substance introduced into the reaction vessel, the discharge power and the like.

In the present invention, it is preferable that the photoconductive layer 303 contains atoms for controlling conductivity as necessary. The atoms for controlling the conductivity may be contained in the photoconductive layer 303 in a state of being distributed uniformly and uniformly, or there may be a part containing the atoms in the layer thickness direction in a non-uniform distribution state. Is also good.

The atoms controlling the conductivity include so-called impurities in the semiconductor field.
An atom belonging to Group IIIb of the Periodic Table giving p-type conduction characteristics (hereinafter abbreviated as “IIIb group atom”) or an atom belonging to Group Vb of the Periodic Table giving n-type conduction characteristics (hereinafter “Vb Group Vb”). Atom ").

As the Group IIIb atoms, specifically, boron (B), aluminum (Al), gallium (Ga),
There are indium (In), thallium (Tl) and the like, and B, Al and Ga are particularly preferable. Group Vb atoms include:
Specifically, phosphorus (P), arsenic (As), antimony (S
b), bismuth (Bi) and the like, and P and As are particularly preferable.

The content of the atoms for controlling the conductivity contained in the photoconductive layer 303 is preferably 1 × 10 ^-2 to 1
It is desirable that the concentration be 00 atomic ppm, more preferably 5 × 10 ⁻² to 50 atomic ppm, and most preferably 1 × 10 ⁻¹ to 10 atomic ppm.

Atoms that control conductivity, for example,
In order to structurally introduce a group b atom or a group Vb atom, a source material for introducing a group IIIb atom or a source material for introducing a group Vb atom in a gaseous state into a reaction vessel during layer formation. It may be introduced together with another gas for forming the photoconductive layer 303. As a source material for introducing a Group IIIb atom or a source material for introducing a Group Vb atom, a gaseous material at ordinary temperature and normal pressure or a material which can be easily gasified at least under layer forming conditions is employed. It is desirable.

As such a raw material for introducing a Group IIIb atom, specifically, for introducing a boron atom,
_{2 H 6, B 4 H 10} , B 5 H 9, B 5 H 11, B 6 H 10, B 6 H 12,
Examples include boron hydride such as B ₆ H ₁₄ and boron halide such as BF ₃ , BCl ₃ and BBr ₃ . In addition, AlCl ₃ ,
GaCl ₃ , Ga (CH ₃ ) ₃ , InCl ₃ , TlCl _{3 and the} like can also be mentioned.

Effective as a raw material for introducing group Vb atoms
Used for introducing phosphorus atoms is PH_Three, P_Two
H_FourPhosphorus hydride, PH_FourI, PF_Three, PF_Five, PCl_Three,
PCl_Five, PBr_Three, PBr_Five, PI_ThreeSuch as phosphorous halide
No. In addition, AsH _Three, AsF_Three, AsCl_Three,
AsBr_Three, AsF_Five, SbH_Three, SbF_Three, SbF_Five, S
bCl_Three, SbCl_Five, BiH_Three, BiCl_Three, BiBr_Three
Are also effective starting materials for introducing group Vb atoms.
Can be mentioned.

Further, these raw materials for introducing atoms for controlling conductivity may be diluted with H ₂ and / or He if necessary.

Further, in the present invention, the photoconductive layer 303
It is also effective to include at least one of a carbon atom, an oxygen atom, and a nitrogen atom in the carbon. The content of at least one of carbon atoms, oxygen atoms and nitrogen atoms is preferably 1 × 10 ⁻⁵ to 10 atom%, more preferably 1 × 10 ⁵ %, based on the sum of silicon atoms, carbon atoms, oxygen atoms and nitrogen atoms. ^-4 to
8 at%, optimally 1 × 10 ^{−3 to} 5 at% is desirable.
At least one of a carbon atom, an oxygen atom and a nitrogen atom is
The photoconductive layer may be evenly and uniformly contained, or there may be a portion having a non-uniform distribution such that the content changes in the layer pressure direction of the photoconductive layer.

In the present invention, the layer thickness of the photoconductive layer 303 is not particularly limited, but may be determined as desired from the viewpoint of obtaining desired electrophotographic characteristics and economic effects, but is preferably not limited to 20 to 50 μm. It is more preferably 23 to 45 μm, and most preferably 25 to 40 μm. By setting the layer thickness in the range of 20 to 50 μm,
Electrophotographic characteristics such as charging ability and sensitivity can be further improved, and the production time of the photoconductive layer can be shortened to reduce the production cost.

In the present invention, it is desirable that the second layer region provided on the surface side of the photoconductive layer has a thickness that absorbs 50 to 95% of the incident light. By making the film thicker than the film thickness that absorbs 50% of the incident light, the pre-exposure and image exposure can be more fully absorbed, and the temperature characteristics of sensitivity, the linearity of sensitivity, and the effect of preventing optical memory can be more fully exhibited. it can.

When the second layer region is provided also on the support side of the photoconductive layer, the thickness is desirably 0.05 to 5 μm. If the thickness is less than 0.05 μm, the effect of improving adhesion and preventing roughening may not be sufficiently exhibited, and if it exceeds 5 μm, the level of the effect of preventing image deletion may decrease.

In order to achieve the object of the present invention and to form the photoconductive layer 303 having desired film characteristics, the mixing ratio of the gas for supplying Si and the diluent gas, the gas pressure in the reaction vessel, the discharge power, It is necessary to appropriately set the temperature of the support.

H used as a diluent gas_Two And / or
The He flow rate is appropriately selected according to the layer design.
However, in the case of the first layer region, the
H _Two And / or the flow rate of He is usually 0.1
４4 times, preferably 0.2 to 3.5 times, optimally 0.5 times
It is desirable to control the range to up to three times, and the second layer region
In the case of, H_Two And / or He
Is usually 0.5 to 10 times, preferably 1 to 10 times.
It is desirable to control it within the range of 8 times, optimally 2 to 6 times.
No.

The optimum range of the gas pressure in the reaction vessel is similarly appropriately selected according to the layer design.
0 ^{−2 to} 2 × 10 ³ Pa, preferably 5 × 10 ^{−2 to} 5 × 1
It is preferably 0 ² Pa, most preferably 1 × 10 ⁻¹ to 2 × 10 ² Pa.

Similarly, the optimum range of the discharge power is appropriately selected according to the layer design. The ratio of the discharge power to the flow rate of the gas for supplying Si is set to 0.3 to 5, preferably 0.5 to 0.5.
-4, optimally, it is desirable to set it in the range of 1-3.

Further, an optimum range of the temperature of the support 301 is appropriately selected according to the layer design.
Preferably from 200 to 350 ° C, more preferably from 210 to
Desirably, the temperature is 340 ° C, and most preferably, 220 to 330 ° C. It is desirable that the temperature of the support during the formation of the second layer region is higher than the temperature of the support during the formation of the first layer region.

In the present invention, the preferable ranges of the temperature of the support and the gas pressure for forming the photoconductive layer include the above-mentioned ranges, but the conditions are not usually independently determined separately. It is desirable to determine the optimum value based on mutual and organic relationships to form a light receiving member having desired properties. <Surface Layer> In the present invention, it is preferable to further form an amorphous silicon-based surface layer 304 on the photoconductive layer 303 formed on the support 301 as described above, if necessary. This surface layer 304 is the free surface 31
It is provided appropriately to achieve the object of the present invention mainly in moisture resistance, continuous repeated use characteristics, electrical pressure resistance, use environment characteristics, and durability.

Also, in the present invention, since each of the amorphous materials forming the photoconductive layer 303 and the surface layer 304 forming the light receiving layer 302 has a common component of silicon atoms, The chemical stability is sufficiently ensured at the lamination interface.

The surface layer 304 can be made of any material as long as it is an amorphous silicon material. For example, the surface layer 304 contains a hydrogen atom (H) and / or a halogen atom (X) and further contains a carbon atom. Amorphous silicon (a-SiC: H, X), amorphous silicon containing a hydrogen atom (H) and / or a halogen atom (X), and further containing an oxygen atom (a-SiO: H, X), a hydrogen atom ( H) and / or amorphous silicon (a-Si) containing a halogen atom (X) and further containing a nitrogen atom.
N: H, X), amorphous silicon (a-SiCON: H, X) containing a hydrogen atom (H) and / or a halogen atom (X) and further containing at least one of a carbon atom, an oxygen atom and a nitrogen atom. ) Are suitably used.

In the present invention, in order to effectively achieve the object, the surface layer 304 is formed by a vacuum deposition film formation method by appropriately setting numerical conditions of film formation parameters so as to obtain desired characteristics. Is done. Specifically, for example, a glow discharge method (an AC discharge CVD method such as a low-frequency CVD method, a high-frequency CVD method or a microwave CVD method, or a DC discharge CVD method), a sputtering method, a vacuum deposition method,
It can be formed by various thin film deposition methods such as an ion plating method, a photo CVD method, and a thermal CVD method. These thin film deposition methods are appropriately selected and adopted depending on factors such as manufacturing conditions, the degree of load under capital investment, the manufacturing scale, and the characteristics desired for the light receiving member to be produced. It is preferable to use a deposition method equivalent to that of the photoconductive layer from the viewpoint of properties.

For example, a-Si
In order to form the surface layer 304 made of C: H, X, a source gas for supplying Si that can supply silicon atoms (Si) and a source gas for supplying C that can supply carbon atoms (C) are basically used. A raw material gas and a raw material gas for supplying H that can supply hydrogen atoms (H) or / and a raw material gas for X supply that can supply halogen atoms (X) are placed in a reaction vessel capable of reducing the pressure inside a desired reaction vessel. Introduced in a gaseous state, a glow discharge is generated in the reaction vessel, and a-SiC: H, X is formed on a support 301 on which a photoconductive layer 303 previously formed at a predetermined position is formed.
May be formed.

The material of the surface layer used in the present invention may be any amorphous material containing silicon, but is preferably a compound with a silicon atom containing at least one element selected from carbon, nitrogen and oxygen. Particularly, those containing a-SiC as a main component are preferable.

When the surface layer is composed mainly of a-SiC, the amount of carbon is preferably in the range of 30% to 90% with respect to the sum of silicon atoms and carbon atoms.

In the present invention, it is necessary that the surface layer 304 contains hydrogen atoms and / or halogen atoms, which compensates for dangling bonds of silicon atoms,
It is indispensable for improving the layer quality, especially for improving the photoconductive properties and the charge retention properties. In general, the hydrogen content is desirably 30 to 70 atomic%, preferably 35 to 65 atomic%, and most preferably 40 to 60 atomic%, based on the total amount of the constituent atoms. The content of the halogen atom is usually 0.01 to 15 atomic%, preferably 0.1 to 15 atomic%.
It is desirable that the content be 1 to 10 atomic%, optimally 0.6 to 4 atomic%.

The light-receiving member formed within the above range of the content of hydrogen and / or halogen atom can be applied as a far superior material which has never been seen before. That is, it is known that defects (mainly dangling bonds of silicon atoms and carbon atoms) existing in the surface layer adversely affect the characteristics as a light receiving member for electrophotography. For example, deterioration of charging characteristics due to injection of charge from the free surface, fluctuations in charging characteristics due to changes in the surface structure under the use environment, for example, high humidity, and further from the photoconductive layer to the surface layer from the photoconductive layer during corona charging or light irradiation As an adverse effect, the charge is injected and the charge is trapped in the defect in the surface layer to cause an afterimage phenomenon at the time of repeated use.

Therefore, by controlling the hydrogen content in the surface layer to 30 atomic% or more, the defects in the surface layer are greatly reduced, and as a result, the electric characteristics and the high-speed continuous usability are reduced as compared with the conventional case. Dramatic improvement can be achieved.

On the other hand, if the hydrogen content in the surface layer exceeds 70 atomic%, the hardness of the surface layer is reduced, so that it may not be able to withstand repeated use. Therefore, in order to cope with more repeated use, controlling the hydrogen content in the surface layer within the above range is a very important factor in obtaining a significantly excellent desired electrophotographic property. One. The hydrogen content in the surface layer can be controlled by the flow rate (ratio) of the raw material gas, the temperature of the support, the discharge power, the gas pressure, and the like.

By controlling the content of halogen atoms in the surface layer to 0.01 atomic% or more, the generation of bonds between silicon atoms in the surface layer and other atoms, for example, carbon atoms can be more effectively reduced. Can be achieved. further,
As a function of the halogen atoms in the surface layer, it is possible to more effectively prevent the bond between the silicon atom and the carbon atom or the like from being broken by the damage of the corona or the like.

On the other hand, if the content of halogen atoms in the surface layer exceeds 15 atomic%, the effect of the generation of bonds between silicon atoms and carbon atoms in the surface layer and the effect of silicon atoms and carbon atoms due to damage by corona and the like will occur. There is a limit in improving the effect of preventing the bond breaking, and further, since excess halogen atoms hinder the traveling properties of carriers in the surface layer,
In some cases, the residual potential and the image memory are remarkably recognized. Therefore, controlling the content of halogen atoms in the surface layer within the above range is one of the important factors for obtaining desired electrophotographic characteristics. The content of halogen atoms in the surface layer can be controlled by the flow rate (ratio) of the raw material gas, the temperature of the support, the discharge power, the gas pressure, and the like, similarly to the hydrogen content.

The substance which can be a gas for supplying silicon (Si) used in forming the surface layer of the present invention includes:
Silicon hydrides (silanes) in a gas state such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ or the like, which can be gasified, can be used effectively. SiH ₄ and SiH ₆ are preferable in terms of good Si supply efficiency in terms of easy handling and good Si supply efficiency. Further, these Si supply source gases may be diluted with a gas such as H ₂ , He, Ar, Ne or the like as necessary.

Examples of the substance that can serve as a carbon supply gas include:
A gaseous hydrocarbon such as CH ₄ , C ₂ H ₂ , C ₂ H ₆ , C ₃ H ₈ , C ₄ H ₁₀ , or a gasifiable hydrocarbon can be used effectively. Easy handling, Si
CH ₄ , C ₂ H ₂ , and C ₂ H ₆ are preferred in terms of good supply efficiency and the like. Further, the raw material gas for supplying C may be used after being diluted with a gas such as H ₂ , He, Ar, or Ne as necessary.

Substances that can be nitrogen or oxygen supply gas include NH ₃ , NO, N ₂ O, NO ₂ , O ₂ , CO, C
Compounds in a gaseous state or gasifiable such as O ₂ and N ₂ are mentioned as being effectively used. In addition, these nitrogen and oxygen supply source gases may be replaced with H ₂ ,
It may be used after being diluted with a gas such as He, Ar, or Ne.

In order to make it easier to control the introduction ratio of hydrogen atoms introduced into the surface layer 304 to be formed, these gases may further be hydrogen gas or silicon compound gas containing hydrogen atoms. Also, it is preferable to form a layer by mixing desired amounts. Further, each gas is not limited to a single species, and a plurality of species may be mixed at a predetermined mixture ratio.

As the effective source gas for supplying a halogen atom, a gaseous or gasizable halogen compound such as a halogen gas, a halide, an interhalogen compound containing a halogen, a silane derivative substituted with a halogen, or the like is preferably mentioned. . Further, a gaseous or gasifiable silicon hydride compound containing a halogen atom, which contains a silicon atom and a halogen atom as constituent elements, can also be mentioned as an effective compound. Specific examples of the halogen compound that can be suitably used in the present invention include fluorine gas (F ₂ ), BrF, ClF, ClF ₃ , BrF ₃ , and Br.
Inter-halogen compounds such as F ₅ , IF ₃ and IF ₇ can be mentioned. As a silicon compound containing a halogen atom, that is, a silane derivative substituted with a so-called halogen atom, specifically, for example, silicon fluoride such as SiF ₄ or Si ₂ F ₆ can be preferably mentioned.

In order to control the amount of hydrogen atoms and / or halogen atoms contained in the surface layer 304, for example, the temperature of the support 301, a raw material used to contain hydrogen atoms and / or halogen atoms The amount to be introduced into the reaction vessel, the discharge power and the like may be controlled.

At least one of carbon atoms, oxygen atoms and nitrogen atoms may be uniformly contained in the surface layer, or may be non-uniform such that the content changes in the thickness direction of the surface layer. There may be a portion having a distribution.

Further, in the present invention, it is preferable that the surface layer 304 contains atoms for controlling conductivity as necessary. The atoms controlling the conductivity may be contained in the surface layer 304 in a state of being uniformly distributed,
Alternatively, there may be portions contained in a non-uniform distribution state in the layer thickness direction.

Examples of the atoms for controlling the conductivity include so-called impurities in the field of semiconductors. A group IIIb atom giving p-type conductivity or a group Vb atom giving n-type conductivity is used. Can be.

Examples of Group IIIb atoms include boron (B), aluminum (Al), gallium (Ga),
There are indium (In), thallium (Tl) and the like, and B, Al and Ga are particularly preferable. Group Vb atoms include:
Specifically, phosphorus (P), arsenic (As), antimony (S
b), bismuth (Bi) and the like, and P and As are particularly preferable.

The content of atoms controlling conductivity contained in the surface layer 304 is preferably 1 × 10 ⁻³ to 1 ×.
10 ³ atomic ppm, more preferably 1 × 10 ^{-2 to} 5 × 1
Desirably, the concentration is 0 ² atomic ppm, most preferably 1 × 10 ^-1 to 1 × 10 ² atomic ppm. Atoms controlling conductivity,
For example, in order to structurally introduce a group IIIb atom or a group Vb atom, a source material for introducing a group IIIb atom or a source material for introducing a group Vb atom is reacted in a gaseous state during layer formation. What is necessary is just to introduce into the container with another gas for forming the surface layer 304. As a source material for introducing a Group IIIb atom or a source material for introducing a Group Vb atom, a gaseous material at ordinary temperature and normal pressure or a material which can be easily gasified at least under layer forming conditions is employed. It is desirable. As such a raw material for introducing a Group IIIb atom, specifically, for introducing a boron atom, B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ , B ₅ H ₁₁ , B
_{6 H 10, B 6 H 12} , B 6 borohydride of H _14, etc., BF _3, BC
l _3, BBr ₃ boron halides, etc., and the like. In addition, AlCl ₃ , GaCl ₃ , Ga (CH ₃ ) ₃ , InC
l ₃ , TlCl _{3 and the} like can also be mentioned.

As a raw material for introducing a group Vb atom, it is effective to use PH ₃ ,
Phosphorus hydride such as P ₂ H ₄ , PH ₄ I, PF ₃ , PF ₅ , PC
and phosphorus halides such as l ₃ , PCl ₅ , PBr ₃ , PBr ₅ and PI ₃ . In addition, AsH ₃ , AsF ₃ , AsC
l ₃ , AsBr ₃ , AsF ₅ , SbH ₃ , SbF ₃ , Sb
F ₅ , SbCl ₃ , SbCl ₅ , BiH ₃ , BiCl ₃ , B
iBr _{3 and the} like can also be mentioned as effective starting materials for introducing Group Vb atoms.

Further, these raw materials for introducing atoms for controlling conductivity may be diluted with a gas such as H ₂ , He, Ar, Ne or the like, if necessary.

The thickness of the surface layer 304 in the present invention may be such that the purpose of providing the surface layer in combination with the light receiving layer can be achieved, and is usually 0.01 to 3 μm, preferably 0.05 to 0.05 μm. It is desirable that the thickness be set to .about.2 .mu.m, optimally 0.1 to 1 .mu.m. If the layer thickness exceeds 3 μm, the effect on the electrophotographic characteristics due to an increase in the residual potential and the like will be observed.

The surface layer 304 according to the present invention is carefully formed so that its required characteristics are provided as desired. That is, Si, C and / or N and / or O,
The substance containing H and / or X as a constituent element takes a form structurally from crystalline to amorphous depending on its forming conditions, and has electrical properties from conductivity to semiconducting properties and insulating properties. In the present invention, the formation conditions are strictly selected as desired so that a compound having desired characteristics according to the purpose is formed, since the compound exhibits properties from a conductive property to a non-photoconductive property. Is made.

For example, in order to provide the surface layer 304 mainly for the purpose of improving the pressure resistance, the surface layer 304 is formed as a non-single-crystal material having a remarkable electric insulating behavior in a use environment.

When the surface layer 304 is provided mainly for the purpose of improving the characteristics of continuous and repeated use and the characteristics of the use environment, the above-mentioned degree of electric insulation is alleviated to some extent.
It is formed as a non-single-crystal material having a certain sensitivity to the irradiated light.

In order to form the surface layer 304 having characteristics capable of achieving the object of the present invention, it is necessary to appropriately set the gas mixing ratio, the gas pressure in the reaction vessel, the discharge power, and the temperature of the support. However, these layer formation factors are not usually independently determined separately, but it is necessary to determine an optimum value based on mutual and organic relations in order to form a charge injection blocking layer having desired characteristics. desirable.

Further, in the present invention, a blocking layer (lower surface layer) in which the content of carbon atoms, oxygen atoms and nitrogen atoms is smaller than that of the surface layer may be provided between the photoconductive layer and the surface layer, if necessary. It is also effective to further provide characteristics such as charging ability.

A region may be provided between the surface layer 304 and the photoconductive layer 303 in which the content of at least one of carbon atoms, oxygen atoms and nitrogen atoms changes so as to decrease toward the photoconductive layer 303. good. This improves the adhesion between the surface layer and the photoconductive layer, smoothes the movement of the photocarrier to the surface, and reduces the influence of interference due to light reflection at the interface between the photoconductive layer and the surface layer. it can. <Charge Injection Blocking Layer> In the light receiving member of the present invention, a charge injection blocking layer having a function of blocking charge injection from the conductive support side is provided between the conductive support and the photoconductive layer. Is even more effective. That is, the charge injection blocking layer has a function of preventing charge from being injected from the support side to the photoconductive layer side when the photoreceptive layer receives a charging treatment of a fixed polarity on its free surface. Such a function is not exerted when it is subjected to a charging treatment of, for example, has a so-called polarity dependency. In order to provide such a function, the charge injection blocking layer contains a relatively large number of atoms for controlling conductivity as compared with the photoconductive layer.

The atoms for controlling the conductivity contained in the layer may be distributed evenly and uniformly in the layer, or may be uniformly distributed in the thickness direction of the layer, Some portions may be contained in a state of being uniformly distributed. When the distribution concentration is non-uniform, it is preferable that the compound be contained so as to be distributed more on the support side.

However, in any case, it is necessary to uniformly contain the particles in a uniform distribution in the in-plane direction parallel to the surface of the support from the viewpoint of making the characteristics uniform in the in-plane direction. .

The atoms for controlling the conductivity contained in the charge injection blocking layer include so-called impurities in the field of semiconductors.
Group V atoms or Group Vb atoms that provide n-type conduction properties can be used.

As the Group IIIb atom, specifically, B
(Boron), Al (aluminum), Ga (gallium), In (indium), Ta (thallium), and the like, and B, Al, and Ga are particularly preferable. Specific examples of group Vb atoms include P (phosphorus), As (arsenic), and Sb.
(Antimony), Bi (bismuth) and the like.
As is preferred.

In the present invention, the content of atoms for controlling conductivity contained in the charge injection blocking layer is appropriately determined as desired so that the object of the present invention can be effectively achieved. 10-1 × 10 ⁴ atom pp
m, more preferably 50 to 5 × 10 ³ atomic ppm, and most preferably 1 × 10 ^{2 to} 3 × 10 ³ atomic ppm.

Further, the charge injection blocking layer contains carbon atoms,
By containing at least one of a nitrogen atom and an oxygen atom, the adhesion to another layer provided in direct contact with the charge injection blocking layer can be further improved.

The carbon atoms, nitrogen atoms or oxygen atoms contained in the layer may be uniformly distributed in the layer, or may be contained evenly in the layer thickness direction. Some portions may be contained in a non-uniformly distributed state. However, in any case, it is necessary to uniformly contain the particles in a uniform distribution in a plane parallel to the surface of the support from the viewpoint of making the characteristics uniform in the plane.

The content of at least one of carbon atoms, nitrogen atoms and oxygen atoms contained in the entire region of the charge injection blocking layer in the present invention is appropriately determined so that the object of the present invention can be effectively achieved. However, in the case of one kind, the amount is used, and in the case of two or more kinds, the total is preferably 1 ×
It is desirable that the concentration be 10 ⁻³ to 30 atomic%, more preferably 5 × 10 ^{−3 to} 20 atomic%, and most preferably 1 × 10 ⁻² to 10 atomic%.

Further, the hydrogen atoms and / or halogen atoms contained in the charge injection blocking layer in the present invention compensate for dangling bonds existing in the layer, and are effective in improving the film quality.
The content of hydrogen atoms and / or halogen atoms in the charge injection blocking layer (i.e., the content of the sum of hydrogen atoms and halogen atoms, and when these are included alone, their contents are preferably 1) -50 atomic%, more preferably 5-4
Desirably, it is 0 atomic%, and optimally 10 to 30 atomic%.

In the present invention, the thickness of the charge injection blocking layer may be appropriately selected from the viewpoints of obtaining desired electrophotographic characteristics and economical effects, and is preferably 0.1 to 5 μm.
m, more preferably 0.3-4 μm, optimally 0.5-
Desirably, it is 3 μm. By setting the layer thickness in this range, the ability to prevent injection of charges from the support is further improved,
It is possible to obtain a more sufficient charging ability, to further improve the electrophotographic characteristics, and to shorten the manufacturing time and reduce the manufacturing cost.

In the present invention, to form the charge injection blocking layer, a vacuum deposition method similar to the above-described method of forming the photoconductive layer can be employed.

In order to form the charge injection blocking layer 305 having characteristics capable of achieving the object of the present invention, it is necessary to appropriately set the gas mixing ratio, the gas pressure in the reaction vessel, the discharge power, and the temperature of the support. However, these layer formation factors are not usually independently determined separately, but are determined optimally based on mutual and organic relations to form a charge injection blocking layer having desired characteristics. It is desirable.

In addition, in the light receiving member of the present invention, at least an aluminum atom, a silicon atom, a hydrogen atom and / or
And a layer region in which atoms are contained in a non-uniform distribution state in the layer thickness direction.

In the light receiving member of the present invention, the support 301 and the photoconductive layer 303 or the charge injection blocking layer 3
For the purpose of further improving the adhesion between the silicon atom and the silicon atom, for example, Si ₃ N ₄ , SiO ₂ , SiO, or a silicon atom as a base, a hydrogen atom and / or a halogen atom, a carbon atom, an oxygen atom, An adhesion layer formed of an amorphous material or the like containing at least one kind of nitrogen atom may be provided. Further, a light absorbing layer for preventing generation of an interference pattern due to light reflected from the support may be provided.

Next, an apparatus and a film forming method for forming a light receiving layer will be described in detail.

FIG. 4 is a schematic configuration diagram showing an example of an apparatus for manufacturing a light receiving member by a high frequency plasma CVD method (RF-PCVD) using a power frequency in an RF band. FIG.
Is as follows.

This apparatus is roughly classified into a deposition apparatus (410)
0), a source gas supply device (4200), a reaction vessel (4
111) is constituted by an exhaust device (not shown) for reducing the pressure inside. A cylindrical support (4112), a heater for heating the support (4113), and a raw material gas introduction pipe (411) are provided in a reaction vessel (4111) in the deposition apparatus (4100).
4) is installed, and a high-frequency matching box (41)
15) is connected.

The source gas supply device (4200) is made of SiH
_{4, GeH 4, H 2,} CH 4, B 2 H 6, PH 3 or the like material gas cylinders (4221 to 4226) and valve (42
31-4236, 4241-4246, 4251-42
56) and mass flow controllers (4211-4)
216), and a cylinder for each source gas is connected to a gas introduction pipe (4114) in the reaction vessel (4111) via a valve (4260).

The formation of a deposited film using this apparatus can be performed, for example, as follows. First, the reaction vessel (4
111), a cylindrical support (4112) is set therein, and the reaction vessel (4112) is evacuated by an exhaust device (not shown) (for example, a vacuum pump).
111) is evacuated. Subsequently, the temperature of the cylindrical support (4112) is controlled to a predetermined temperature of 200 ° C. to 350 ° C. by the support heating heater (4113).

A source gas for forming a deposited film is supplied to a reaction vessel (41).
11), the gas cylinder valve (423)
1-4236), a leak valve of the reaction vessel (4117)
Is closed, and the inflow valve (42
41 to 4246), outflow valves (4251 to 425)
6) After confirming that the auxiliary valve (4260) is open, first open the main valve (4118) and exhaust the reaction vessel (4111) and the inside of the gas pipe (4116).

Next, the reading of the vacuum gauge (4119) was about 1 × 1.
When the pressure becomes 0 ^-2 Pa, the auxiliary valve (4260) and the outflow valves (4251 to 4256) are closed.

Thereafter, gas cylinders (4221 to 422)
From 6), each gas is introduced by opening valves (4231 to 4236), and each gas pressure is adjusted to ² kg / cm ² by a pressure regulator (4261 to 4266). Next, the inflow valves (4241 to 4246) are gradually opened to introduce each gas into the mass flow controllers (4211 to 4216).

After the preparation for film formation is completed as described above, each layer is formed in the following procedure.

When the temperature of the cylindrical support (4112) reaches a predetermined temperature, necessary ones of the outflow valves (4251 to 4256) and the auxiliary valve (4260) are gradually opened, and a predetermined amount is opened from the gas cylinders (4221 to 4226). Of the reaction vessel (411) through the gas introduction pipe (4114).
Introduce in 1). Next, the mass flow controller (4
221 to 4216) are adjusted so that each source gas has a predetermined flow rate. At this time, while watching the vacuum gauge (4119), the main valve (4111) is adjusted so that the pressure in the reaction vessel (4111) becomes a predetermined pressure of 1.5 × 10 ² Pa or less.
18) Adjust the opening. When the internal pressure becomes stable, an RF power supply (not shown) having a frequency of 13.56 MHz is set to a desired power, and a high-frequency matching box (4115)
RF power is introduced into the reaction vessel (4111) through
Generates glow discharge. The raw material gas introduced into the reaction vessel is decomposed by this discharge energy, and a deposited film containing silicon as a main component is formed on the cylindrical support (4112). After the formation of the desired film thickness, the supply of the RF power is stopped, the outflow valve is closed to stop the gas from flowing into the reaction vessel, and the formation of the deposited film is completed.

By repeating the same operation a plurality of times, a light receiving layer having a desired multilayer structure is formed.

When forming each layer, it goes without saying that all outflow valves other than the necessary gas are closed, and each gas is supplied to the reaction vessel (411).
1) Close the outflow valves (4251-4256), open the auxiliary valve (4260), and open the main valve to avoid remaining in the piping from the outflow valves (4251-4256) to the reaction vessel (4111). Valve (41
The operation of fully opening 18) and once evacuating the system to a high vacuum is performed as necessary.

In order to make the film formation uniform, it is also effective to rotate the support (4112) at a predetermined speed by a driving device (not shown) during the layer formation.

Further, it goes without saying that the above-mentioned gas types and valve operations are changed according to the conditions for forming each layer.

In any of the methods, the temperature of the support at the time of forming the deposited film is in particular 200 ° C. to 350 ° C., preferably 210 ° C. to 340 ° C., more preferably 220 ° C. to 340 ° C.
It is desirable that the temperature be higher than or equal to 330 ° C.

The heating method of the support may be a heating element which uses vacuum, and more specifically, an electric resistance heating element such as a winding heater of a sheath heater, a plate heater, a ceramic heater, a halogen lamp, an infrared lamp, or the like. Examples of the heating element include a heat radiation lamp heating element such as a lamp, and a heating element using a liquid or a gas as a heating medium and a heat exchange unit. As the surface material of the heating means, metals such as stainless steel, nickel, aluminum, and copper, ceramics, heat-resistant polymer resins, and the like can be used.

In addition, a method is also used in which a container dedicated to heating is provided in addition to the reaction container, and after heating, the support is transferred into the reaction container in a vacuum.

[0154]

EXAMPLES The effects of the present invention will be specifically described below with reference to examples.

<Example 1> Using the apparatus for manufacturing a light receiving member shown in FIG. 4, a charge injection blocking layer and light were applied on an 80 mm-diameter mirror-finished aluminum cylinder (support) under the conditions shown in Table 1. A light receiving member comprising a conductive layer and a surface layer was produced. At this time, the first layer region from the charge injection blocking layer side,
The photoconductive layer was formed in the order of the second layer region.

[0156]

[Table 1] On the other hand, instead of the aluminum cylinder, using a cylindrical sample holder provided with a groove for mounting a sample substrate, forming each layer region of the photoconductive layer on a glass substrate (Corning 7059) and a Si wafer. Under these conditions, an a-Si film having a thickness of about 1 μm was deposited. The deposited film on the glass substrate has an optical band gap (Eg)
Is measured, a skewer electrode of Cr is vapor-deposited, the characteristic energy (Eu) of the exponential function tail is measured by CPM, and the hydrogen content (Ch) of the deposited film on the Si wafer is measured by FTIR.
Was measured.

In the example shown in Table 1, Ch, Eg,
Eu is 20 atomic%, 1.75 eV and 69 meV, respectively.
In the second layer region, Ch, Eg, and Eu are each 1
5 atomic%, 1.72 eV and 52 meV.

Next, without changing the thickness of each layer region,
H ₄ gas flow rate, mixing ratio of SiH ₄ gas and H ₂ gas, S
By varying the ratio of the iH ₄ gas flow rate to the discharge power and the support temperature, the Eg (C
h) Various light receiving members having different Eus were produced.

The light-receiving member thus produced was set in an electrophotographic apparatus (NP-6550 manufactured by Canon Inc. was modified for experiments).
The potential characteristics were evaluated.

At this time, the process speed was 380 mm / s
ec, pre-exposure (700 nm LED) 4lux · s
ec, current value of charging wire of corona charger 1000μ
Under the condition of A, the surface potential (dark potential) of the light receiving member in a dark state was measured by a potential sensor of a surface voltmeter (Model 344 manufactured by TREK) set at the developing device position of the electrophotographic apparatus. Next, charging conditions were set so that the dark potential was 400 V at room temperature, an LED having a peak wavelength of 680 nm was used as an image exposure light source, and the amount of exposure was changed by changing the exposure amount.
The V characteristic (curve) was measured. Thereafter, the surface temperature of the light receiving member is reduced to 45 by a drum heater included in the light receiving member.
The temperature was raised to ° C, and the EV characteristic (curve) was measured in the same manner to evaluate the temperature characteristic of sensitivity and the linearity of sensitivity. In addition, the memory potential was determined by using a 680 nm LED as an image exposure light source in the same manner as the sensitivity measurement. The difference from the potential was measured.

FIGS. 5, 6 and 7 show the relationship between Eg and Eu and the temperature characteristics of sensitivity, the linearity of sensitivity, and the memory, respectively. Each characteristic is shown as a relative value when 1 is set when the photoconductive layer is entirely composed of only the first layer region. Therefore, it can be said that there is an improvement effect in using the second layer region when the number is less than one (the same applies to the following embodiments).

As is clear from FIGS. 5, 6 and 7, Eg is 1.65 eV or more in the second layer region.
It has been found that when the temperature is 75 eV or less and Eu is 50 meV or more and 60 meV or less, favorable characteristics can be obtained in all of the temperature characteristics of sensitivity, the linearity of sensitivity, and the evaluation at the memory potential.

<Embodiment 2> Using an apparatus for manufacturing a light receiving member shown in FIG. 4 and under the conditions shown in Table 1 in the same manner as in Embodiment 1, an aluminum cylinder (support) having a mirror surface having a diameter of 80 mm was processed. A light receiving member composed of a charge injection blocking layer, a photoconductive layer, and a surface layer was manufactured by changing the thickness of the second layer region of the photoconductive layer, that is, the ratio of absorbing incident light.

The potential characteristics of the individual light-receiving members produced were evaluated in the same manner as in Example 1.

FIG. 8 shows the relationship between the ratio of absorbing incident light when changing the thickness of the second layer region of the photoconductive layer of this example, the temperature characteristic of sensitivity, the linearity of sensitivity, and the memory potential. , FIG. 9 and FIG. Each characteristic is shown as a relative value when 1 is set when the photoconductive layer is constituted only by the first layer region. As is clear from FIGS. 8, 9 and 10, when the second layer region of the photoconductive layer has a thickness absorbing 50% to 95% of the incident light, the temperature characteristic of sensitivity and the linearity of sensitivity are obtained. In addition, it was found that good characteristics could be obtained both in evaluation at the memory potential.

<Embodiment 3> Using the apparatus for manufacturing a light-receiving member shown in FIG. 4, a charge injection blocking layer under the conditions shown in Table 2 was placed on an aluminum cylinder (support) having a mirror-finished surface with a diameter of 80 mm. A light receiving member comprising a photoconductive layer and a surface layer was produced. At this time, the second layer region from the charge injection blocking layer side,
The first layer region and the second layer region were stacked in this order.

[0167]

[Table 2] In the example of Table 2, Ch, Eg, and Eu in the first layer region are 20 atomic%, 1.75 eV, and 69 meV, respectively.
Is 15 atomic% for each of Ch, Eg and Eu,
It was 1.72 eV and 52 meV.

[0168] Then, in the same manner as in Example 1, without changing the thickness of each layer region, the mixing ratio of SiH ₄ gas flow rate, SiH ₄ gas and H ₂ gas, and the ratio of SiH ₄ gas flow rate to discharge power Various light-receiving members having different Eg (Ch) and Eu in the second layer region were produced by changing the temperature of the support in various ways.

The potential characteristics of each of the produced light receiving members were evaluated in the same manner as in Example 1, and the image characteristics were evaluated with respect to the density distribution of a solid black image, ie, the so-called roughness, and Eu of the second layer region was 50 meV. It was found that under the conditions of 60 meV or less, good characteristics can be obtained in all of the sensitivity temperature characteristics, the sensitivity linearity, the evaluation at the memory potential, and the prevention of roughening.

<Embodiment 4> Using the apparatus for manufacturing a light-receiving member shown in FIG. 4, under the same conditions as in Embodiment 3, charge injection prevention was performed on a mirror-finished aluminum cylinder (support) having a diameter of 80 mm. A light receiving member comprising a layer, a photoconductive layer and a surface layer was prepared. Then, various light receiving members were manufactured by changing the thickness of the second layer region provided on the blocking layer side.

With respect to each of the produced light receiving members, the same characteristic evaluation and image deletion as in Example 3 were performed.

FIG. 1 shows the relationship between the thickness of the second layer region on the blocking layer side in the present example, the roughness, and the image deletion rank.
1 and FIG. In each case, the relative values are shown assuming that the case where the photoconductive layer is composed of only the first layer region is 1.

As is clear from FIGS. 11 and 12, when the second layer region is disposed on the support side, the ratio of the second layer region to the photoconductive layer is 0.1 μm or more and 5 μm or less. It was also found that both the effects of preventing roughness and image deletion were good.

Further, the diameter of the support was 60 mm, 30 m
When the light receiving member was produced under the conditions shown in Table 2 with the value of m being small, no image defect was observed in any case.

<Embodiment 5> A charge injection blocking layer, a photoconductive layer, and a surface layer were formed on a mirror-finished aluminum cylinder (support) having a diameter of 80 mm using the apparatus for manufacturing a light receiving member shown in FIG. A light receiving member was manufactured. On this occasion,
The photoconductive layer is in the order of the first layer region and the second layer region from the charge injection blocking layer side, and the content of silicon atoms and carbon atoms in the surface layer is shown in FIG. As shown in a), a surface layer having a non-uniform distribution in the layer thickness direction was provided.

Table 3 shows the conditions for manufacturing the light receiving member at this time.

[0177]

[Table 3] In this example, Ch, Eg, and Eu in the first layer region of the photoconductive layer are used.
Are respectively 18 atomic%, 1.74 eV, 65 meV,
As for Ch, Eg, and Eu in the second layer region, the results were 15 atomic%, 1.73 eV, and 54 meV, respectively.

The produced light receiving member was set in an electrophotographic apparatus (a Canon NP-6550 was modified for experiments, and the image exposure was an LED having a peak wavelength of 680 nm), positively charged, and the same potential characteristics as in Example 1 were set. As a result, good results were obtained with respect to charging ability, temperature characteristics of sensitivity, linearity of sensitivity, and memory.

When the produced light-receiving member was positively charged and evaluated for an image, no optical memory was observed on the image, and good characteristics were obtained also in other image characteristics (pockets, image deletion).

That is, the photoconductive layer is arranged in the order of the first layer region and the second layer region from the charge injection blocking layer side, and the content of silicon atoms and carbon atoms in the surface layer is unevenly distributed in the layer thickness direction. Even when the surface layer in the state is provided, Ch and Eg of the photoconductive layer are each set to 10 at% or more and 20 at% or less, 1.65 eV to 1.75 eV, and Eu of the first layer region is set to 60 meV or more. It has been found that it is necessary to obtain Eu in the second layer region of not less than 70 meV and not less than 50 meV and not more than 60 meV in order to obtain good electrophotographic characteristics.

<Embodiment 6> In this embodiment, a mirror-finished aluminum cylinder (support) having a diameter of 108 mm was used, and the photoconductive layer was formed in the first layer region from the charge injection blocking layer side.
In the order of the second layer region, He was used in place of H ₂ in Example 5. Note that the content of silicon atoms and carbon atoms in the surface layer was in a non-uniform distribution state in the layer thickness direction as shown in FIG.

Table 4 shows the conditions for producing the light receiving member at this time.

[0183]

[Table 4] In this example, Ch, Eg, and Eu in the first layer region of the photoconductive layer are used.
Are 15 atomic%, 1.73 eV, 63 meV, respectively.
The results of Ch, Eg, and Eu in the second layer region were 20 atomic%, 1.75 eV, and 56 meV, respectively.

The produced light receiving member was set in an electrophotographic apparatus (NP-6550 manufactured by Canon Inc. was modified for experiments, and the image exposure was an LED having a peak wavelength of 680 nm), positively charged, and evaluated in the same manner as in Example 5. As a result, good electrophotographic properties were obtained as in Example 5.

That is, the photoconductive layer is formed in the order of the first layer region and the second layer region from the charge injection blocking layer side by using He instead of H ₂ , and the surface layer contains silicon atoms and carbon atoms. Even in the case where a surface layer having a non-uniform distribution in the layer thickness direction is provided, the Ch and Eg of the photoconductive layer are each 10 to 20 atomic%, 1.65 eV to 1.
It has been found that it is necessary to obtain a good electrophotographic characteristic by setting the Eu of the first layer region to 60 meV or more and 70 meV or less, and the Eu of the second layer region to 50 meV or more and 60 meV or less.

<Embodiment 7> In this embodiment, an 80 mm diameter mirror-finished aluminum cylinder (support) is used, and the photoconductive layer is formed from the charge injection blocking layer side to the first layer region and the second layer region. , And all the layers contained a fluorine atom, a boron atom, a carbon atom, an oxygen atom, and a nitrogen atom. As shown in FIG. 14A, a surface layer was provided in which the content of silicon atoms and carbon atoms in the surface layer was unevenly distributed in the layer thickness direction.

Table 5 shows the conditions for producing the light receiving member at this time.

[0188]

[Table 5] In this example, Ch, Eg, and Eu in the first layer region of the photoconductive layer are used.
Are respectively 20 atomic%, 1.74 eV, 70 meV,
As for Ch, Eg, and Eu in the second layer region, the results were 18 atomic%, 1.74 eV, and 58 meV, respectively.
An electrophotographic device (Canon NP-
6550 modified for experiment, image exposure is 680n peak wavelength
m), positively charged and evaluated in the same manner as in Example 5. As a result, good electrophotographic characteristics were obtained as in Example 5.

That is, the photoconductive layer is arranged in the order of the first layer region and the second layer region from the charge injection blocking layer side, and the content of silicon atoms and carbon atoms in the surface layer is unevenly distributed in the layer thickness direction. Even when a surface layer in a state is provided and all layers contain a fluorine atom, a boron atom, a carbon atom, an oxygen atom, and a nitrogen atom, each of Ch and Eg of the photoconductive layer is 10 atom% to 20 atom each. % Or less, 1.65 eV
Is set to 1.75 eV or less and Eu in the first layer region is set to 60
not less than meV and not more than 70 meV;
It has been found that it is necessary to set the voltage between meV and 60 meV to obtain good electrophotographic properties.

<Embodiment 8> In this embodiment, a mirror-finished aluminum cylinder (support) having a diameter of 108 mm was used, and the photoconductive layer was placed in the first layer region from the charge injection blocking layer side.
In the order of the second layer region, an intermediate layer (an upper blocking layer) is provided between the photoconductive layer and the surface layer, in which the content of carbon atoms is smaller than that of the surface layer and the atoms for controlling conductivity are contained. Was.

Table 6 shows the conditions for manufacturing the light receiving member at this time.

[0192]

[Table 6] In this example, Ch, Eg, and Eu in the first layer region of the photoconductive layer are used.
Are respectively 13 atomic%, 1.72 eV, 65 meV,
Ch, Eg, and Eu in the second layer region were 12 atomic%, 1.7 eV, and 50 meV, respectively.

The produced light receiving member was set in an electrophotographic apparatus (NP-6550 manufactured by Canon Inc. was modified for experiments, and the image exposure was an LED having a peak wavelength of 680 nm), negatively charged, and evaluated in the same manner as in Example 5. As a result, good electrophotographic characteristics were obtained as in Example 5.

That is, the photoconductive layer is arranged in the order of the first layer region and the second layer region from the charge injection blocking layer side, and the carbon atom content is set between the photoconductive layer and the surface layer. Reduce,
Even when an intermediate layer (upper blocking layer) containing atoms for controlling conductivity is provided, the Ch and Eg of the photoconductive layer are each set to 10 at% or more and 20 at% or less to 1.65 eV.
Is set to 1.75 eV or less and Eu in the first layer region is set to 60
not less than meV and not more than 70 meV;
It has been found that it is necessary to set the voltage between meV and 60 meV to obtain good electrophotographic properties.

<Embodiment 9> In this embodiment, a mirror-finished aluminum cylinder (support) having a diameter of 80 mm was used, and the photoconductive layer was formed in the second layer region and the first layer region from the charge injection blocking layer side. Then, a surface layer was provided in which fluorine atoms were contained in all the layers and the contents of silicon atoms and carbon atoms were in a non-uniform distribution state in the layer thickness direction.

Table 7 shows the conditions for producing the light receiving member at this time.

[0197]

[Table 7] In this example, Ch, Eg, and Eu in the first layer region of the photoconductive layer are used.
Are 16 atomic%, 1.74 eV, 64 meV, respectively.
The results of Ch, Eg, and Eu in the second layer region were 16 atomic%, 1.73 eV, and 53 meV, respectively.

The produced light-receiving member was set in an electrophotographic apparatus (NP-6550 manufactured by Canon Inc. was modified for experiments, and the image exposure was an LED having a peak wavelength of 680 nm), positively charged, and evaluated in the same manner as in Example 5. As a result, good electrophotographic characteristics were obtained as in Example 5.

When the produced photoreceptor member was positively charged and the image was evaluated, no optical memory was observed on the image, and the other image characteristics (pocking, roughening, and prevention of image deletion) were good. Photographic properties were obtained, and especially the anti-graininess was at a very good level.

That is, the photoconductive layer has a configuration in which the second layer region, the first layer region, and the second layer region are arranged in this order from the charge injection blocking layer side, and all the layers contain fluorine atoms. Even when a surface layer is provided in which the contents of silicon atoms and carbon atoms are in a non-uniform distribution state in the layer thickness direction, Ch and Eg of the photoconductive layer are each at least 10 atomic% or more.
It is preferable to set the electrophotographic characteristics to 0 atomic% or less, 1.65 eV to 1.75 eV, Eu in the first layer region to 60 meV to 70 meV, and Eu in the second layer region to 50 meV to 60 meV. It turned out to be necessary to get.

Example 10 In this example, a mirror-finished aluminum cylinder (support) having a diameter of 60 mm was used, and the photoconductive layer was formed in the second layer region from the charge injection blocking layer side.
The first layer region and the second layer region are arranged in this order, and in addition to H ₂ , H
e was used. The content of silicon atoms and carbon atoms in the surface layer was made to be non-uniformly distributed in the layer thickness direction as shown in FIG.

Table 8 shows the manufacturing conditions of the light receiving member at this time.

[0203]

[Table 8] In this example, Ch, Eg, and Eu in the first layer region of the photoconductive layer are used.
Are respectively 13 atomic%, 1.72 eV, 70 meV,
Ch, Eg, and Eu in the second layer region were 12 atomic%, 1.71 eV, and 57 meV, respectively.

The produced light receiving member was set in an electrophotographic apparatus (NP-6550 manufactured by Canon Inc. was modified for experiments, and the image exposure was an LED having a peak wavelength of 680 nm), positively charged, and evaluated in the same manner as in Example 5. As a result, good electrophotographic characteristics were obtained as in Example 5.

When the produced photoreceptor member was positively charged and the image was evaluated, no optical memory was observed on the image, and the other image characteristics (pocketing, roughening, and prevention of image deletion) were good. Photographic properties were obtained, and the level of anti-roughness was particularly good.

That is, using a mirror-finished aluminum cylinder (support) having a diameter of 60 mm, the photoconductive layer was formed from the charge injection blocking layer side to the second layer region, the first layer region, and the second layer region. Even when He is used in addition to H ₂ , Ch and Eg of the photoconductive layer are each set to 10 at% to 20 at% and 1.65 eV to 1.75 eV, respectively. Eu of layer region is 60me
V to 70 meV, Eu of the second layer region is 50 me
It has been found that it is necessary to set V to 60 meV or less in order to obtain good electrophotographic characteristics.

<Embodiment 11> In this embodiment, the diameter is 108 mm.
Aluminum cylinder with mirror finish (support)
And the photoconductive layer is arranged in the order of the second layer region, the first layer region, and the second layer region from the charge injection blocking layer side, and nitrogen atoms instead of carbon atoms are used as atoms constituting the surface layer. It was provided so as to be contained in the surface layer.

Table 9 shows the conditions for producing the light receiving member at this time.

[0209]

[Table 9] In this example, Ch, Eg, and Eu in the first layer region of the photoconductive layer are used.
Are respectively 18 atomic%, 1.73 eV, 65 meV,
As for Ch, Eg, and Eu in the second layer region, the results were 19 atomic%, 1.74 eV, and 55 meV, respectively.

The produced photoreceptor member was set in an electrophotographic apparatus (an NP-6550 manufactured by Canon Inc. was modified for experiments, and the image exposure was an LED having a peak wavelength of 680 nm), positively charged, and evaluated in the same manner as in Example 5. As a result, good electrophotographic characteristics were obtained as in Example 5.

When the produced photoreceptor member was positively charged and the image was evaluated, no optical memory was observed on the image, and the image characteristics were good with respect to other image characteristics (pocketing, roughening, and prevention of image deletion). Photographic properties were obtained, and the level of anti-roughness was particularly good.

That is, the photoconductive layer is formed in the order of the second layer region, the first layer region, and the second layer region from the charge injection blocking layer side, and nitrogen constituting the surface layer is replaced by nitrogen instead of carbon atom. Even when a surface layer containing atoms is provided,
Ch and Eg of the photoconductive layer are respectively 10 atomic% or more and 20 atomic% or less, 1.65 eV or more and 1.75 eV or less, Eu of the first layer region is 60 meV or more and 70 meV or less, and Eu of the second layer region is 50 meV or less. It has been found that it is necessary to set the voltage to 60 meV or less in order to obtain good electrophotographic characteristics.

Example 12 In this example, a mirror-finished aluminum cylinder (support) having a diameter of 30 mm was used, and the photoconductive layer was formed in the second layer region from the charge injection blocking layer side.
The first layer region and the second layer region were arranged in this order.

Table 10 shows the conditions for producing the light receiving member at this time.

[0215]

[Table 10] In this example, Ch, Eg, and Eu in the first layer region of the photoconductive layer are used.
Are respectively 20 atomic%, 1.75 eV, 68 meV,
Ch, Eg, and Eu in the second layer region were 12 atomic%, 1.7 eV, and 51 meV, respectively.

The produced photoreceptor was set in an electrophotographic apparatus (GP-55 manufactured by Canon Inc. was modified for experiments, and the image exposure was an LED having a peak wavelength of 680 nm), positively charged, and evaluated in the same manner as in Example 5. As a result, good electrophotographic characteristics were obtained as in Example 5.

When the produced photoreceptor member was positively charged and the image was evaluated, no optical memory was observed on the image, and good image characteristics (prevention of spotting, roughening, and image deletion) were obtained. Photographic properties were obtained, and the level of anti-roughness was particularly good.

That is, an aluminum cylinder (support) having a diameter of 30 mm was used as the support, and the photoconductive layer was placed in the second layer region, the first layer region, and the second layer region from the charge injection blocking layer side.
Even in the case of the order of the layer regions, Ch, of the photoconductive layer,
Eg is 10 atomic% or more and 20 atomic% or less, respectively, 1.6
5 eV or more and 1.75 eV or less, and Eu in the first layer region
From 60 meV to 70 meV, and Eu in the second layer region
It has been found that it is necessary to obtain a good electrophotographic property in the range of 50 to 60 meV.

[0219]

According to the present invention, the temperature characteristics of the light receiving member in the operating temperature range can be remarkably improved and the occurrence of optical memory can be substantially eliminated. An electrophotographic light-receiving member is provided which has improved stability in a use environment, can clearly obtain halftones, and can stably obtain high-quality images with high resolution.

Therefore, by providing the electrophotographic light-receiving member of the present invention with the above-mentioned characteristics, a-S
It can solve all the problems in the conventional electrophotographic light-receiving member composed of i, and exhibits particularly excellent electrical properties, optical properties, photoconductive properties, image properties, durability and use environment properties. .

In particular, in the present invention, by providing a layer region having a small optical band gap and a small characteristic energy on the surface side of the photoconductive layer, a semiconductor laser or LE
When D is used as an exposure light source, a change in sensitivity to a change in ambient temperature is suppressed, and the device has extremely excellent potential characteristics and image characteristics.

Further, by providing a layer region having a narrow optical band gap and a small characteristic energy on the blocking layer side of the photoconductive layer, minute unevenness in image density is suppressed and extremely excellent potential characteristics and image characteristics are obtained. It has the characteristics that it has characteristics and that the adhesion to the support is improved, making it easy to apply to a small-diameter support.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of an example of a sub-gap light absorption spectrum of a-Si for explaining characteristic energy of an exponential function tail in the present invention.

FIG. 2 is a schematic view of an example of an exposure dose-surface potential (EV) curve of an a-Si photosensitive member for explaining the temperature characteristic of sensitivity and the linearity of sensitivity in the present invention.

FIG. 3 is a schematic layer configuration diagram for explaining a layer configuration of a preferred embodiment of the light receiving member of the present invention.

FIG. 4 is a schematic explanatory view of an example of an apparatus for forming a light receiving layer of the light receiving member of the present invention, which is an apparatus for manufacturing a light receiving member by a glow discharge method using an RF band high frequency power supply.

FIG. 5 is a diagram showing the relationship between the optical band gap (Eg) and characteristic energy (Eu) of the second layer region of the photoconductive layer and the temperature characteristics of sensitivity in the light receiving member of the present invention.

FIG. 6 is a diagram showing a relationship between the optical band gap (Eg) and characteristic energy (Eu) of the second layer region of the photoconductive layer in the light receiving member of the present invention and the linearity of sensitivity.

FIG. 7 is a diagram showing the relationship between the optical band gap (Eg) and characteristic energy (Eu) of the second layer region of the photoconductive layer and the memory in the light receiving member of the present invention.

FIG. 8 is a diagram showing the relationship between the thickness of the layer region (the ratio of incident light absorption) of the second layer region of the photoconductive layer in the light receiving member of the present invention and the temperature characteristic of sensitivity.

FIG. 9 is a diagram showing the relationship between the thickness of the layer region of the second layer region of the photoconductive layer (the ratio of absorption of incident light) and the linearity of sensitivity in the light receiving member of the present invention.

FIG. 10 shows a second example of the photoconductive layer in the light receiving member of the present invention.
FIG. 4 is a diagram showing the relationship between the thickness of the layer region (the ratio of absorption of incident light) of the layer region and the memory.

FIG. 11 is a diagram showing the relationship between the ratio of the second layer region to the photoconductive layer in the light receiving member of the present invention and the temperature characteristic of sensitivity.

FIG. 12 is a diagram showing the relationship between the ratio of the second layer region in the photoconductive layer in the light receiving member of the present invention and the density distribution (graininess) of a solid black image.

FIGS. 13 (a) and (b) show Examples 5 and 6, respectively.
FIG. 3 is a diagram showing a distribution of silicon atom and carbon atom contents [C / (Si + C)] in the surface layer in FIG.

FIGS. 14 (a) and (b) show Examples 7 and 1, respectively.
FIG. 4 is a diagram showing the distribution of the content [C / (Si + C)] of silicon atoms and carbon atoms in the surface layer at 0.

[Explanation of symbols]

 Reference Signs List 300 light receiving member 301 conductive support 302 light receiving layer 303 photoconductive layer 304 surface layer 305 charge injection blocking layer 311 first layer region 312 second layer region 310 free surface 4100 deposition device 4111 reaction vessel 4112 cylindrical support Body 4113 Supporting heater 4114 Raw material gas introduction pipe 4115 Matching box 4116 Raw material gas pipe 4117 Reaction vessel leak valve 4118 Main exhaust valve 4119 Vacuum gauge 4200 Raw material gas supply device 4211-4216 Mass flow controller 4221-4226 Raw material gas cylinder 4231-4236 Raw material Gas cylinder valve 4241-4246 Gas inflow valve 4251-4256 Gas outflow valve 4261-4266 Pressure regulator

Continuation of front page (72) Inventor Daisuke Tazawa 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc.

Claims (10)

[Claims] 1. A conductive support, provided on the conductive support, containing a hydrogen atom and / or a halogen atom,
A photoconductive layer made of a non-single-crystal material having silicon atoms as a base, wherein the photoconductive layer has a hydrogen atom and / or halogen atom content (Ch), an optical band The equation (10) is such that the gap (Eg) is 10 atomic% or more and 20 atomic% or less, 1.65 eV or more and 1.75 eV or less, the photon energy (hν) is an independent variable, and the absorption coefficient (α) of the light absorption spectrum is a dependent variable I) The first layer region and the second layer region having different characteristic energies (Eu) obtained from the linear relationship portion (exponential function tail) of the function represented by lnα = (1 / Eu) · hν + α ₁ (I) And Eu in the first layer region is 60 meV or more and 70 meV.
Eu of the second layer region is 50 meV or more and 6 or less.
A light-receiving member for electrophotography, which is 0 meV or less. 2. The photoconductive layer has a configuration in which the first layer region and the second layer region are arranged in this order from the conductive support side, and The light receiving member for electrophotography according to claim 1, wherein the film thickness is a thickness that absorbs 50% to 95% of incident light. 3. The photoconductive layer, wherein the second layer region has a layer thickness of 0.1 to 5 μm from the conductive support side,
2. The electrophotograph according to claim 1, wherein the first layer region and the second layer region having a thickness that absorbs 50% to 95% of incident light are arranged in this order. 3. Light receiving member. 4. The photoreceptor for electrophotography according to claim 1, wherein the photoconductive layer contains at least one element belonging to Group IIIb or Group Vb of the periodic table. Element. 5. The electrophotographic light-receiving member according to claim 1, wherein the photoconductive layer contains at least one of carbon, oxygen and nitrogen. 6. A surface layer made of a silicon-based non-single-crystal material containing a hydrogen atom and / or a halogen atom and containing at least one of carbon, oxygen and nitrogen is provided on the photoconductive layer. The light receiving member for electrophotography according to claim 1. 7. The photoconductive layer is a non-monolayer containing silicon atoms as a base material and containing at least one of carbon, oxygen and nitrogen and at least one element selected from Group IIIb or Vb of the periodic table. It is provided on the charge injection blocking layer made of a crystalline material, and further has hydrogen atoms and / or
6. A photoreceptor for electrophotography according to claim 1, wherein a surface layer comprising a silicon-based non-single-crystal material containing a halogen atom and containing at least one of carbon, oxygen and nitrogen is provided. Element. 8. The surface layer has a thickness of 0.01 to 3
The light receiving member for electrophotography according to claim 6, wherein the thickness is μm. 9. The charge injection blocking layer has a layer thickness of 0.1.
The electrophotographic light-receiving member according to claim 7, wherein the thickness is 1 to 5 μm. 10. The photoconductive layer has a thickness of 20 to 50 μm.
The electrophotographic light-receiving member according to any one of claims 1 to 9, wherein